JP2000155434A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the electrophotographic photoreceptor high in sensitivity and chargeability and practicable for a high-speed copying machine and also for a laser printer by using a specified tetrazaporphyrin compound as the charge generating material of the photoreceptor. SOLUTION: The photosensitive layer of the photoreceptor contains the tetrazaporphyrin compound represented by formula I in which at least one of A-E is a group represented by formula II and at least one of them is a group represented by formula III; and M is a metal atom or a metal oxide or metal hydroxide or metal halide group, and in formulae II and III, each or r1-r6 is an H or halogen atom or an optionally substituted alkyl or such aryl or such cycloalkyl or nitro group, or r1 and r2, and any couple of r3-r6 may combine with each other to form a ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptor for electrophotography, and more particularly to a novel tetraazaporphyrin compound as a substance which generates charge carriers when irradiated with light (hereinafter referred to as "charge generating substance"). The present invention relates to an electrophotographic photosensitive member provided with a photosensitive layer containing

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as selenium, cadmium sulfide, and zinc oxide have been used as photoconductive materials for photoconductors used in electrophotography. The term "electrophotographic method" as used herein generally means that a photoconductive photoreceptor is first charged in a dark place, for example, by corona discharge, and then subjected to image exposure to selectively dissipate the charges in only the exposed portions, and then statically. An image forming method in which an electrostatic latent image is obtained, and the latent image portion is developed with a detection fine particle (toner) composed of a colorant such as a dye or a pigment and a polymer substance to form a visible image. One. The basic characteristics required of the photoreceptor in such an electrophotographic system include (1) being able to be charged to an appropriate potential in a dark place, (2) having little charge dissipation in a dark place, and (3). Charge can be quickly dissipated by light irradiation, and the like.

At present, the above-mentioned inorganic substances have various advantages as well as various advantages. For example, the selenium photoreceptor is difficult to manufacture, its production cost is high, it is difficult to process it into a belt because it is not flexible, and it is sensitive to heat and mechanical shock, so care must be taken when handling it. Disadvantages such as the need for Cadmium sulfide and zinc oxide are used as a photoreceptor by being dispersed in a resin as a binder.
Due to mechanical defects such as smoothness, hardness, tensile strength and friction resistance, it cannot be used repeatedly as it is.

In recent years, electrophotographic photoreceptors using various organic substances have been proposed to eliminate the disadvantages of these inorganic substances, and some of them have been put to practical use. For example, poly
A photoreceptor comprising N-vinylcarbazole and 2,4,7-trinitrofluoren-9-one (US Pat. No. 348)
4237), a photoconductor obtained by sensitizing poly-N-vinylcarbazole with a pyrylium salt-based dye (described in JP-B-48-25658), and a photoconductor containing an organic pigment as a main component (described in JP-B-48-25658). Representative examples thereof include a photoreceptor having a eutectic complex consisting of a dye and a resin (described in JP-A-47-10735). In particular, a laminated photoreceptor in which a thin film of an organic pigment is formed on a conductive support (a charge generation layer) and a layer mainly composed of a charge transport substance (a charge transport layer) is formed thereon, is a conventional organic photoreceptor. Exhibiting higher sensitivity than the photoreceptor
Active research has been conducted on the basis of the abundance of material variations.

On the other hand, in the copying industry, etc., in recent years, there has been a demand for an editing function and a complex processing function, and with this, non-impact printer technology has been developed, and it has been applied to laser printers, laser facsimile machines, digital copiers and the like. Digital recording devices that can be seen are becoming widespread. Semiconductor lasers are often used as light sources in digital recording devices because of their small size, low cost, and simplicity, but the oscillation wavelength of semiconductors currently used is limited to a wavelength range of 600 nm or more. Have been. Therefore, the electrophotographic photosensitive member used in these recording apparatuses is required to have photosensitivity in a wavelength region of at least 600 to 850 nm.

As organic photoconductive materials satisfying this requirement, phthalocyanine pigments, azo pigments, cyanine pigments, azulene pigments, squarium pigments and the like are known.
In particular, phthalocyanine pigments have spectral absorption up to a relatively long wavelength region, have photosensitivity, and have various variations depending on the type of central metal and crystal type. Research is being actively carried out. Known phthalocyanine pigments include ε-type copper phthalocyanine, X-type metal-free phthalocyanine, τ-type metal-free phthalocyanine, vanadyl phthalocyanine, and titanyloxyphthalocyanine (JP-A-8-231869, JP-A-5-6659).
No. 5, JP-B No. 8-13942, etc.), but in reality, it has not been able to obtain satisfactory ones in terms of sensitivity, charging ability, repetition durability and the like. Also, registered patent No. 2637487 discloses a tetraazaporphyrin derivative.
No satisfactory satisfactory in chargeability, repetition durability and the like has been obtained.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member which can be practically used not only for high-speed copying machines but also for laser printers.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a novel tetraazaporphyrin compound useful as a charge generating material for an electrophotographic photoreceptor and completed the present invention. I came to. That is, according to the present invention, first, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, at least the following general formula (1) is contained in the photosensitive layer; ) A,
An electrophotographic photoreceptor comprising a tetraazaporphyrin compound wherein at least one of B, D and E is A2 and at least one is A1 is provided.

Embedded image

Embedded image

Embedded image (In A1, A2, r ₁ ~r ₆ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group or a nitro group, r ₁ And r ₂ and r ₃ to r ₆ may form a ring with each other.
M represents a metal atom, a metal oxide, a metal hydroxide or a metal halide. Second, in an electrophotographic photoreceptor having a photosensitive layer on a conductive support, at least one of the general formula (1)
Wherein at least one of A, B, D and E in the general formula (1) is A2 and at least one is A1
And a tetraazaporphyrin compound wherein all of A, B, D and E in the formula (1) are A2. Third, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the photosensitive layer is represented by at least the general formula (1), and A, B, D, A tetraazaporphyrin compound wherein at least one of E is A2 and at least one is A1, and a tetraazaporphyrin compound wherein all of A, B, D and E in the general formula (1) are A1 The present invention provides an electrophotographic photoreceptor characterized by containing.
Fourth, in an electrophotographic photoreceptor having a photosensitive layer on a conductive support, at least one of the general formula (1)
Wherein at least one of A, B, D and E in the general formula (1) is A2 and at least one is A1
A tetraazaporphyrin compound represented by the general formula (1), a tetraazaporphyrin compound wherein all of A, B, D and E in the general formula (1) are A2;
An electrophotographic photoreceptor characterized by containing a tetraazaporphyrin compound wherein D and E are all A1. Fifth, in an electrophotographic photoreceptor having a photosensitive layer on a conductive support, the photosensitive layer is represented by at least the following general formula (2), and in the general formula (2), A, B,
An electrophotographic photoreceptor comprising a tetraazaporphyrin compound wherein at least one of D and E is A2 and at least one is A1 is provided.

Embedded image

Embedded image

Embedded image (In A1, A2, r ₁ ~r ₆ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group or a nitro group, r ₁ And r ₂ and r ₃ to r ₆ may form a ring with each other.) Sixth, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, at least one of the general formula (2)
Wherein at least one of A, B, D and E in the general formula (2) is A2 and at least one is A1
And a tetraazaporphyrin compound wherein all of A, B, D and E in the general formula (2) are A2. Seventh, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the photosensitive layer is represented by at least the general formula (2), and in the general formula (2), A, B, D, A tetraazaporphyrin compound wherein at least one of E is A2 and at least one is A1, and a tetraazaporphyrin compound wherein all of A, B, D and E in the general formula (2) are A1 The present invention provides an electrophotographic photoreceptor characterized by containing.
Eighth, in an electrophotographic photoreceptor having a photosensitive layer on a conductive support, at least one of the general formula (2)
Wherein at least one of A, B, D and E in the general formula (2) is A2 and at least one is A1
A tetraazaporphyrin compound represented by the general formula (2), a tetraazaporphyrin compound wherein all of A, B, D and E in the general formula (2) are A2;
An electrophotographic photoreceptor characterized by containing a tetraazaporphyrin compound wherein D and E are all A1. Ninth, the photosensitive layer according to any one of the above first to eighth aspects comprises a charge generation layer containing a charge generation substance and a charge transport layer containing a charge transport substance, and the charge generation layer The present invention further provides an electrophotographic photoreceptor comprising a tetraazaporphyrin compound represented by the general formula (1) or (2) described in any of the above first to eighth. Tenth, in the electrophotographic photoreceptor described in the ninth aspect, the photosensitive layer comprises a charge generation layer containing a charge generation substance, and a charge transport layer containing a hole transport substance. A negatively charged electrophotographic photoreceptor characterized by being provided on a body is provided. Eleventhly, there is provided an electrophotographic photoreceptor wherein the hole transporting substance is a stilbene-based compound represented by the following general formula (3).

Embedded image (Wherein, R ₁ and R ₂ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R ₃ and R ₄ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted Represents an aryl group or a heterocyclic group.
₁ and R ₂ may form a ring with each other. Ar ₁ represents a substituted or unsubstituted arylene group or a heterocyclic group. Twelfth, in the electrophotographic photoreceptor according to the ninth aspect, the photosensitive layer includes a charge generation layer containing a charge generation substance;
A positive charge type electrophotographic photoreceptor is provided, wherein a charge transport layer containing an electron transport material is provided on a conductive support in this order. Thirteenth, in the photoconductor according to the twelfth aspect, the electron transporting material is (2,3-diphenyl-1-indenylidene) malononitrile represented by the following formula (4). A photographic photoreceptor is provided.

Embedded image Fourteenth, the photosensitive layer described in any one of the first to eighth above is a tetravalent compound represented by the general formula (1) or (2) described in any one of the first to eighth as a charge generating substance. An electrophotographic photoreceptor characterized by being a single layer containing an azaporphyrin compound is provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the tetraazaporphyrin compound represented by the general formula (1) of the present invention, M in the general formula (1) is, for example, Cu, TiO, Mg, Co, Pb,
VO, Fe, Zn, Ge, Sn, Ni, Al, Ga, M
Examples include metal atoms such as o and In, metal oxides, metal hydroxides, and metal halides.

In A1 and A2, r _{1 to} r ₆ represent a hydrogen atom, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted cycloalkyl Represents a group, and examples of the halogen atom include a chlorine atom and a fluorine atom. Examples of the alkyl group include a methyl group, an ethyl group, and a t-butyl group, and examples of the substituent include a halogen atom such as a chlorine atom and a fluorine atom, a nitro group, and a cyano group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the substituent include a halogen atom such as a chlorine atom and a fluorine atom, an alkyl group such as a methyl group, an ethyl group and a t-butyl group, a nitro group, and a cyano group. And the like. Examples of the cycloalkyl group include a cyclohexyl group and the like. Examples of the substituent include a halogen atom such as a chlorine atom and a fluorine atom, an alkyl group such as a methyl group, an ethyl group and a t-butyl group, a nitro group, and a cyano group. And the like.
Further, r ₁ and r ₂ and r ₃ to r ₆ may form a ring with each other.

The 2,3-dicyanopyrazine derivative represented by the following general formula (5), which is a precursor of the tetraazaporphyrin compound represented by the general formulas (1) and (2) of the present invention, has the following reaction Synthesized by

Embedded image (Wherein, r ₁ and r ₂ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group or a nitro group, and r ₁ and r 2 ₂ may form a ring with each other.)

The above reaction is usually carried out without solvent, or with an alcoholic solvent such as ethanol and butanol, an aromatic solvent such as benzene, toluene and nitrobenzene, a halogenated solvent such as dichlorobenzene and trichlorobenzene, and an acidic solvent such as acetic acid. It is performed by heating in the presence.
The reaction is preferably performed in the presence of an acidic catalyst such as acetic acid, sulfuric acid, and hydrochloric acid for the purpose of improving the reaction yield and the solubility of the raw materials. The reaction temperature is usually between room temperature and 300 ° C.
It is preferable to perform the reaction at 0 ° C to 200 ° C from the viewpoint of the reaction yield.

A phthalonitrile derivative represented by the following general formula (6) and 1,3,3 represented by the following general formula (7)
-A diiminoisoindoline derivative is a phthalocyanine-
Chemistry and Function-Obtained by known methods described by Shirai and Kobayashi, but some compounds are commercially available.

Embedded image

Embedded image (Wherein, r _{3 to} r ₆ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group or a nitro group, and r _{3 to} r _{6 6} may form a ring with each other.)

The tetraazaporphyrin compound represented by the general formula (1) includes a 2,3-dicyanopyrazine derivative represented by the general formula (5) and a phthalonitrile derivative represented by the general formula (6), or The above general formula (5)
And a 1,3-diiminoisoindoline derivative represented by the general formula (7), and a metal or a compound having a metal together with no solvent or α-chloronaphthalene, dichlorobenzene, In the presence of halogen solvents such as trichlorobenzene, alcohol solvents such as pentanol and octanol, amine solvents such as N, N-dimethylformamide and N-methylpyrrolidone, and aromatic solvents such as benzene, toluene and nitrobenzene. It can be obtained by reacting. Also,
The reaction may be carried out, if necessary, with urea, formamide, 1,8-diazabicyclo [5.4.0] -7-undecene (DB
The reaction may be performed in the presence of an amine catalyst such as U). Here, the mixing ratio (molar ratio) of the compound of the general formula (5) and the compound of the general formula (6) or the compound of the general formula (5) and the compound of the general formula (7) is 0.001: 99.999. ~ 99.
999: 0.001, preferably 0.1: 99.9-9
Preferably, the ratio is 9.9: 0.1 (molar ratio). When the mixing ratio of the compound of the general formula (5) is lower than the above-mentioned mixing ratio and the mixing ratio of the compound of the general formula (6) or the compound of the general formula (7) is higher than the above-mentioned mixing ratio, the residual in the electrophotographic characteristics is obtained. There is a possibility that the potential may increase and the chargeability may decrease. Conversely, when the mixing ratio of the compound of the general formula (5) is higher than the above-mentioned mixing ratio and the mixing ratio of the compound of the general formula (6) or the compound of the general formula (7) is lower than the above-mentioned mixing ratio, electrophotography is performed. There is a possibility that the chargeability may decrease in the characteristics. Although the detailed reason is unknown, the compounds of the general formula (5) and the compound of the general formula (6) or the compound of the general formula (5) and the compound of the general formula (7) are mixed and reacted as raw materials. It has been found that the tetraazaporphyrin compound represented by the general formula (1) obtained by the above greatly improves the chargeability and sensitivity. Further, as the above-mentioned metal, specifically, for example, Mg, Li, and Na, and as the compound having a metal, for example, TiCl ₄ , CoCl ₂ ,
Metal halides such as CuCl ₂ and CuCl, and Ti (O
Alkoxy metals such as Bu) ₄ and Mg (OEt) ₂ . The reaction temperature is usually between room temperature and 300 ° C.
It is preferable to perform the reaction at 0 ° C to 250 ° C from the viewpoint of the reaction yield.

The tetraazaporphyrin compound represented by the general formula (2) includes the 2,3-dicyanopyrazine derivative represented by the general formula (5) and the phthalonitrile derivative represented by the general formula (6), or Of a 2,3-dicyanopyrazine derivative represented by the general formula (5) and a 1,3-diiminoisoindoline derivative represented by the general formula (7) without solvent, α-chloronaphthalene, dichlorobenzene, trichlorobenzene Halogen solvents such as pentanol, alcohol solvents such as pentanol and octanol, N, N-
It can be obtained by reacting in the presence of an amine solvent such as dimethylformamide and N-methylpyrrolidone and an aromatic solvent such as benzene, toluene and nitrobenzene. The reaction may be carried out in the presence of an amine catalyst such as urea, formamide, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), if necessary. Here, the compound of the general formula (5) and the general formula (6)
Or the mixing ratio of the compound of the general formula (5) and the compound of the general formula (7) is 0.001: 99.999 to 9
9.999: 0.001 (molar ratio), preferably 0.1:
It is preferably 99.9 to 99.9: 0.1 (molar ratio). When the mixing ratio of the compound of the general formula (5) is lower than the above-mentioned mixing ratio and the mixing ratio of the compound of the general formula (6) or the compound of the general formula (7) is higher than the above-mentioned mixing ratio, the residual in the electrophotographic characteristics is obtained. There is a possibility that the potential may increase and the chargeability may decrease. Conversely, when the mixing ratio of the compound of the general formula (5) is higher than the above-mentioned mixing ratio and the mixing ratio of the compound of the general formula (6) or the compound of the general formula (7) is lower than the above-mentioned mixing ratio, electrophotography is performed. There is a possibility that the chargeability may decrease in the characteristics. Although the detailed reason is unknown, the compounds of the general formula (5) and the compound of the general formula (6) or the compound of the general formula (5) and the compound of the general formula (7) are mixed and reacted as raw materials. It has been found that the tetraazaporphyrin compound represented by the general formula (2) obtained by the above greatly improves the chargeability and sensitivity. The reaction temperature is usually from room temperature to 300 ° C., particularly preferably from 100 ° C. to 250 ° C., from the viewpoint of the reaction yield.

Table 1 shows examples of these reaction routes, but the present invention is not limited thereto.

[0017]

[Table 1]

Further, the tetraazaporphyrin compound represented by the general formula (1), wherein M = Mg, Li, or Na, is treated in an acidic solvent to obtain the tetraazaporphyrin compound represented by the general formula (2). It is possible to obtain a tetraazaporphyrin compound in high yield.

Specific examples of the compound represented by the general formula (1) include those shown in Tables 2 to 5. Specific examples of the compound represented by the general formula (2) include, for example, What is shown in Tables 6-9 is mentioned.

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

[Table 4]

[0023]

[Table 5]

[0024]

[Table 6]

[0025]

[Table 7]

[0026]

[Table 8]

[0027]

[Table 9]

The tetraazaporphyrin compounds represented by the general formulas (1) and (2) obtained as described above are:
For example, various treatments can be performed to reduce the particle size of the pigment, improve dispersibility, and improve the purity. Examples of such a treatment method include an acid treatment, a solvent treatment, and a milling treatment. The acid treatment is a treatment of dissolving or dispersing the pigment in an acid such as sulfuric acid or the like, and then dropping the pigment on ice water to precipitate a crystal of the pigment, and obtaining crystals by means such as filtration. Is a stirring and stirring treatment of the pigment in a solvent at room temperature or under heating, and the milling treatment is, for example, using a mill such as a sand mill using a glass bead, a steel bead, an alumina ball, or a ball mill. This is the process to be performed. Examples of the solvent used for the solvent treatment include alcohol solvents such as methanol and ethanol; ketone solvents such as cyclohexanone and methyl ethyl ketone; ether solvents such as n-butyl ether, ethylene glycol n-butyl ether and tetrahydrofuran; Amine solvents such as dimethylformamide, N-methylpyrrolidone and quinoline, and water. Alternatively, a mixed system of these solvents can be used. As a solvent used for the milling treatment, for example, methanol,
Alcohol solvents such as ethanol, cyclohexanone,
Ketone solvents such as methyl ethyl ketone; ether solvents such as n-butyl ether, ethylene glycol n-butyl ether and tetrahydrofuran; amine solvents such as N, N-dimethylformamide and N-methylpyrrolidone;
Basic solvents such as quinoline and pyridine; and water.

The tetraazaporphyrin compounds represented by the general formulas (1) and (2) used in the present invention may be used, for example, by mixing and dispersing them with the following pigments. Examples of such organic pigments include C.I. Pigment Blue 25 (color index CI21).
180), CI Pigment Red 41 (CI212
00), CI Acid Red 52 (CI4510
0), CI Basic Red 3 (CI4521)
0), an azo pigment having a carbazole skeleton (JP-A-53
95033), an azo pigment having a distyrylbenzene skeleton (Japanese Patent Application Laid-Open No. 53-133445), an azo pigment having a triphenylamine skeleton (described in Japanese Patent Application Laid-Open No. 53-132347), dibenzothiophene Azo pigments having a skeleton (described in JP-A-54-21728), azo pigments having an oxadiazole skeleton (described in JP-A-54-12742), and azo pigments having a fluorenone skeleton (described in JP-A-54-12742) No. 22834), azo pigments having a bisstilbene skeleton (described in JP-A-54-17733), and azo pigments having a distyryloxadiazole skeleton (described in JP-A-54-21)
No. 29), an azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-14967)
Azo pigments such as, for example, C.I. Pigment Blue 16 (CI74100), phthalocyanine-based pigments such as titanyl phthalocyanine, and further, for example, indigo-based pigments such as C.I. Examples include perylene pigments such as Argoscarlet B (manufactured by Bayer), and Insence Scarlet R (manufactured by Bayer). These organic pigments may be used alone or in combination of two or more.

In the present invention, a dispersion-type or function-separation-type electrophotographic photoreceptor can be prepared by using the organic pigment represented by the general formula (1) or (2) as a charge generating substance and combining it with a charge transporting substance. . In the case of a dispersion type layer structure, a photosensitive layer in which a charge generating substance and a charge transporting substance are dispersed in a binder is provided on a conductive support. In the case of the function separation type, a charge generation layer containing a charge generation substance and a binder is formed on a support, and a charge transport layer containing a charge transport substance and a binder is formed thereon. In this case, the charge generation layer and the charge transport layer may be stacked in reverse order.

Further, in the electrophotographic photosensitive member of the present invention,
An intermediate layer (for example, an undercoat layer) may be provided between the photosensitive layer and the conductive support in order to improve adhesion and charge blocking properties. A protective layer may be provided on the photosensitive layer to improve the quality.

The charge generating substance can be provided by dissolving or dispersing it in an appropriate solvent together with a binder resin, if necessary, coating and drying. Examples of the method for dispersing the charge generating substance include a ball mill, an ultrasonic wave, and a homomixer, and examples of the application method include a dipping coating method, a blade coating method, and a spray coating method.

When the charge generation material is dispersed to form the charge generation layer, the charge generation material is 2 μm or less, preferably 1 μm, in order to improve the dispersibility in the charge generation layer.
Those having the following average particle size are preferred. However, if the particle size is too small, it tends to aggregate rather than increase, the resistance of the charge generation layer increases, the number of crystal defects increases, the sensitivity and repetition characteristics decrease, or there is a limit in miniaturization. Is preferably 0.01 μm.

The solvent used for preparing the dispersion or solution for the charge generation layer or the charge transport layer includes:
For example, N, N-dimethylformamide, toluene, xylene, monochlorobenzene, 1,2-dichloroethane, 1,1,1-trichloroethane, dichloromethane,
1,1,2-trichloroethane, trichloroethylene,
Examples thereof include tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, and butyl acetate.

As the binder used for forming the charge generation layer, the charge transport layer and the dispersion type photosensitive layer, any binder can be used as long as it has good insulating properties, and there is no particular limitation. Specific examples of the binder include, for example, polyethylene, polyvinyl butyral, polyvinyl formal, polystyrene resin, phenoxy resin, polypropylene, acrylic resin,
Methacrylic acid resin, vinyl chloride resin, vinyl acetate resin,
Epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, polyamide resin, silicone resin, addition polymerization type resin such as melamine resin, polyaddition type resin, polycondensation type resin, and repeating units of these resins A copolymer resin containing at least two of the following, for example, vinyl chloride-vinyl acetate copolymer, styrene-acrylic copolymer, vinyl chloride-vinyl acetate-
In addition to an insulating resin such as a maleic anhydride copolymer resin, a polymer organic semiconductor such as poly-N-vinylcarbazole may be used. These binders can be used alone or as a mixture of two or more.

In the case where a photoreceptor is manufactured using the above-described layer constitution and substance, there are preferable ranges of the film thickness and the ratio of the substance. For example, in the case of the negative charge type (lamination of the substrate / charge generation layer / charge transport layer), the charge generation layer has a charge generation substance ratio of 20% by weight and a film thickness of 0.01 in the charge generation layer.
５5 μm is preferred. In the charge transport layer, the ratio of the charge transport material to the binder is preferably 20 to 200% by weight, and the film thickness is preferably 5 to 100 μm. In the case of the positive charge type, in the charge transport layer, the ratio of the charge transport material to the binder is 20 to 200% by weight or more, and the film thickness is 5 to 1%.
It is preferably set to 00 μm. The charge generation layer preferably contains a charge generation substance in an amount of 20% by weight or more based on the binder. Further, the charge generation layer preferably contains a charge transporting substance, which has an effect on suppressing residual potential and improving sensitivity. In this case, the charge transporting material is preferably contained in an amount of 20 to 200% by weight based on the binder. In the case of a so-called dispersion type photoconductor in which a charge generating material and a charge transporting material are dispersed in a binder resin, the ratio of the pigment as the charge generating material to the binder resin in the photosensitive layer is as follows. 5 to 95% by weight, film thickness 1
It is preferably from 0 to 100 μm. In this case, the ratio of the charge transporting substance to the binder resin is preferably 30 to 200% by weight.

In the photosensitive layer, a phenol compound, a hydroquinone compound, a hindered phenol compound, a hindered amine compound, a hindered amine and a hindered amine compound, both of a dispersion type and a function-separation type, are provided for the purpose of improving the chargeability particularly when used repeatedly. A compound in which dophenol is present in the same molecule can be added.

In the present invention, as the conductive support,
Metal plate of aluminum, nickel, copper, titanium, gold, stainless steel, etc., metal drum or metal foil, plastic film on which aluminum, nickel, copper, titanium, tin oxide, indium oxide, etc. are deposited, or paper coated with conductive material And films or drums of plastics and the like.

As the material of the intermediate layer, in addition to the above-mentioned binder resin, polyamide resin, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride Acid copolymer, casein, resin such as N-alkoxymethyl nylon as it is, or tin oxide, aluminum oxide, titanium oxide, silicon oxide, or a dispersion of indium oxide or the like, aluminum oxide, zinc oxide, titanium oxide, Alternatively, a deposition film of silicon oxide or the like can be given.

Further, as the material used for the protective layer, it is appropriate to use the above-mentioned resin as it is, or to disperse a low-resistance substance such as tin oxide or indium oxide. Also, organic plasma polymerized membranes can be used,
The organic plasma polymerized film may optionally contain oxygen, halogen, and atoms of Group III and Group V of the periodic table.

The charge transport material includes a hole transport material and an electron transport material. As the hole transport material, for example, poly-N
Carbazole and its derivatives, poly-γ-carbazolylethyl glutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene,
There are polyvinyl phenanthrene, oxazole derivative, imidazole derivative, triphenylamine derivative and the like,
Among them, a stilbene compound represented by the following general formula (3) is suitably used because of its high charge transport ability.

[0042]

Embedded image (Wherein, R ₁ and R ₂ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R ₃ and R ₄ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted Represents an aryl group or a heterocyclic group.
₁ and R ₂ may form a ring with each other. Ar ₁ represents a substituted or unsubstituted arylene group or a heterocyclic group. )

Specific examples of the stilbene compound represented by the general formula (3) are shown in Tables 8 to 17, but the present invention is not limited thereto.

[0044]

[Table 10]

[0045]

[Table 11]

[0046]

[Table 12]

[0047]

[Table 13]

[0048]

[Table 14]

[0049]

[Table 15]

[0050]

[Table 16]

[0051]

[Table 17]

[0052]

[Table 18]

[0053]

[Table 19]

Examples of the electron transporting substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9.
-Fluorenone, 2,4,5,7-tetranitro-9-
Fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6
8-trinitro-indeno 4H-indeno [1,2-
b] Thiophene-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide and the like, and the following (4), (8) and The electron transporting substances listed in the formula (9) can be suitably used. These charge transport materials are used alone or in combination of two or more.

[0055]

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[0056]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Production Example 1 2,3-dicyano-intermediate represented by the following formula (10)
0.2 mol of 5,6-diphenylpyrazine, 0.2 mol of phthalonitrile, 0.1 mol of cuprous chloride, and 1000 ml of α-chloronaphthalene were stirred and mixed, and the temperature was gradually raised to 200 ° C. under a nitrogen gas stream. From 190 to 2
The mixture was heated and stirred for 3 hours while maintaining the temperature at 10 ° C. After completion of the reaction, the mixture was allowed to cool to 130 ° C., filtered, washed sufficiently with α-chloronaphthalene, further washed several times with methanol, toluene, and water, dried, and dried at a yield of 80% of Cu tetraaza. A porphyrin mixture was obtained.

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Production Example 2 2,3-dicyano-intermediate represented by the above formula (10)
0.2 mol of 5,6-diphenylpyrazine, 0.2 mol of phthalonitrile and 0.1 mol of Ti (OBu) ₄ , 0.2 mol of urea and 1000 ml of octanol were stirred and mixed, and the temperature was gradually raised to 180 ° C. under a nitrogen stream. The mixture was heated and stirred for 3 hours while maintaining the reaction temperature at 180 to 190 ° C. After the completion of the reaction, the reaction solution was allowed to cool to 130 ° C., filtered, washed sufficiently with octanol, further washed several times with methanol, toluene and water, dried, and dried at a yield of 70%.
An O tetraazaporphyrin mixture was obtained.

As a result of mass spectrometry of the obtained TiO tetraazaporphyrin mixture, the exemplified compounds NO, 1-1
Peaks corresponding to ~ NO, 1-5 were observed, and the presence of these compounds was confirmed, indicating that the mixture was a tetraazaporphyrin mixture.

Production Example 3 0.4 mol of metallic Mg, a catalytic amount of iodine and 500 ml of pentanol were mixed by stirring, and gradually heated to 120 ° C. under a nitrogen stream.
The mixture was stirred for 1 hour while maintaining the reaction temperature at 110 to 120 ° C. to activate Mg. After completion of the reaction, the mixture was allowed to cool to room temperature, and then 0.2 mol of 2,3-dicyano-5,6-diphenylpyrazine and 0.2 mol of phthalonitrile, which were intermediates represented by the formula (10), were added thereto.
Stir and mix, gradually raise the temperature to 120 ° C under a nitrogen stream,
The mixture was heated and stirred for 3 hours while maintaining the reaction temperature at 110 to 120 ° C. After completion of the reaction, the reaction solution was left to cool to 80 ° C., filtered, washed sufficiently with pentanol, further washed several times with methanol, toluene, and water, and dried to obtain a yield of 90%.
Of Mg tetraazaporphyrin was obtained.

Production Example 4 40 g of the Mg tetraazaporphyrin mixture obtained in Production Example 3 was added little by little into 3000 ml of trifluoroacetic acid at 5 ° C., and the mixture was stirred for about 1 hour while maintaining the temperature at 5 ° C. or lower. The solution was slowly poured into 10,000 ml of ice water, and the precipitated crystals were filtered. The crystals were washed with distilled water until no acid remained, and dried to obtain a metal-free tetraazavorphyrin mixture in a yield of 90%.

Production Example 5 0.4 mol of metallic Mg, a catalytic amount of iodine and 500 ml of pentanol were mixed with stirring, and gradually heated to 120 ° C. under a nitrogen stream.
The mixture was stirred for 1 hour while maintaining the reaction temperature at 110 to 120 ° C. to activate Mg. After completion of the reaction, the mixture was allowed to cool to room temperature, and then 0.2 mol of an intermediate pyrazine compound represented by the following formula (11) and 0.2 mol of naphthalonitrile were added, mixed with stirring, and gradually stirred under a nitrogen stream. The temperature was raised to 120 ° C, and the mixture was heated and stirred for 3 hours while maintaining the reaction temperature at 110 to 120 ° C. After completion of the reaction, the reaction mixture was allowed to cool to 80 ° C., filtered, washed sufficiently with pentanol, further washed several times with methanol, toluene, and water, dried, and dried with an 80% yield of a Mg tetraazaporphyrin mixture. I got

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As a result of the weight analysis of the Mg tetraazaporphyrin mixture obtained here, the exemplified compound No. 1 was obtained. 3-5, N
o. 4-1 to No. 4 A peak corresponding to the molecular weight of 4-4 was observed, and the presence of these compounds was confirmed, indicating that the mixture was a tetraazaporphyrin mixture.

Production Example 6 Mg tetraazaporphyrin mixture 4 obtained in Production Example 5
0 g was added little by little to 3,000 ml of trifluoroacetic acid at 5 ° C., and the mixture was stirred for about 1 hour while maintaining the temperature at 5 ° C. or lower, then slowly poured into 10,000 ml of ice water, and the precipitated crystals were filtered. The crystals were washed with distilled water until no acid remained, and dried to obtain a metal-free tetraazaporphyrin mixture in a yield of 80%.

As a result of a gravimetric analysis of the obtained metal-free tetraazaporphyrin mixture, the compound No. 14-4,
No. 15-1 to No. 1; A peak corresponding to a molecular weight of 15-4 was observed, and the presence of these compounds was confirmed, indicating that the mixture was a tetraazaporphyrin mixture.

Production Example 7 0.4 mol of metallic Mg, a catalytic amount of iodine and 500 ml of pentanol were mixed by stirring, and gradually heated to 120 ° C. under a nitrogen stream.
The mixture was stirred for 1 hour while maintaining the reaction temperature at 110 to 120 ° C. to activate Mg. After the completion of the reaction, the mixture was allowed to cool to room temperature, and 0.2 mol of 2,3-dicyanopyrazine and 0.2 mol of naphthalonitrile were added.
Stir and mix, gradually raise the temperature to 120 ° C under a nitrogen stream,
The mixture was heated and stirred for 3 hours while maintaining the reaction temperature at 110 to 120 ° C. After the completion of the reaction, the reaction mixture was left to cool to 80 ° C., filtered, washed sufficiently with pentanol, further washed several times with methanol, toluene and water, and then dried to obtain a yield of 75%.
Of Mg tetraazaporphyrin was obtained.

As a result of a weight analysis of the Mg tetraazaporphyrin mixture obtained here, the exemplified compound No. 1 was obtained. 3-1 to N
o. A peak corresponding to the molecular weight of 3-5 was observed, and the presence of these compounds was confirmed, indicating that the mixture was a tetraazaporphyrin mixture.

Production Example 8 Mg tetraazaporphyrin mixture 4 obtained in Production Example 7
0 g was added little by little to 3,000 ml of trifluoroacetic acid at 5 ° C., and the mixture was stirred for about 1 hour while maintaining the temperature at 5 ° C. or lower, then slowly poured into 10,000 ml of ice water, and the precipitated crystals were filtered. The crystals were washed with distilled water until no acid remained, and dried to obtain a metal-free tetraazaporphyrin mixture in a yield of 85%.

As a result of gravimetric analysis of the metal-free tetraazaporphyrin mixture obtained here, the exemplified compound No. 13-1
No. A peak corresponding to a molecular weight of 13-5 is observed,
The presence of these compounds was confirmed and indicated to be a tetraazaporphyrin mixture.

Production Example 9 Intermediate represented by the above formula (10), 2,3-dicyano-
0.06 mol of 5,6-diphenylpyrazine, 0.38 mol of phthalonitrile and 0.1 mol of Ti (OBu) ₄
l, 0.2 mol of urea and 1000 ml of octanol were stirred and mixed, and the temperature was gradually raised to 140 ° C under a nitrogen stream, and the mixture was heated and stirred for 3 hours while maintaining the reaction temperature at 140 to 150 ° C. After the completion of the reaction, the reaction solution was left to cool to room temperature, filtered, washed sufficiently with octanol, further washed several times with toluene and distilled water, and dried to obtain a TiO tetraazaporphyrin mixture having a yield of 65%. .

As a result of the weight analysis of the TiO tetraazaporphyrin mixture obtained here, the exemplified compound No. 1-1 to N
o. A peak corresponding to a molecular weight of 1-5 was observed, and the presence of these compounds was confirmed, indicating that the mixture was a tetraazaporphyrin mixture.

Production Example 10 0.02 mol of 2,3-dicyanopyrazine, 0.38 mol of phthalonitrile and 0.1 mol of Ti (OBu) ₄
0.2 mol of urea and 1000 ml of octanol were stirred and mixed, and the temperature was gradually raised to 140 ° C under a nitrogen stream, and the mixture was heated and stirred for 3 hours while maintaining the reaction temperature at 140 to 150 ° C. After the completion of the reaction, the reaction solution was left to cool to room temperature, filtered, washed sufficiently with octanol, further washed several times with toluene and distilled water, and dried to obtain a TiO tetraazaporphyrin mixture having a yield of 65%. .

As a result of mass spectrometry of the TiO tetraazaporphyrin mixture obtained here, the exemplified compound NO. 2-1
Peaks corresponding to a molecular weight of ~ 2-5 were observed, and the presence of these compounds was confirmed, indicating that the mixture was a tetraazaporphyrin mixture.

Comparative Production Example 1 0.4 mol of metallic Mg, a catalytic amount of iodine and 500 ml of pentanol were stirred and mixed, and gradually heated to 120 ° C. under a nitrogen stream.
The mixture was stirred for 1 hour while maintaining the reaction temperature at 110 to 120 ° C. to activate Mg. After completion of the reaction, the mixture was allowed to cool to room temperature, and then o-dicyanopyrazine was added.
4 mol was added, and the mixture was stirred and mixed.
The temperature was raised to 0 ° C, and the mixture was heated and stirred for 3 hours while maintaining the reaction temperature at 110 to 120 ° C. After the reaction, allow to cool to 80 ℃
After filtration, the mixture was thoroughly washed with pentanol, and further washed several times with methanol, toluene, and water.
It was dried to obtain an 80% -yield Mg tetraazaporphyrin pigment.

This Mg tetraazaporphyrin pigment 40
g was added little by little to 3000 ml of trifluoroacetic acid at 5 ° C., and the mixture was stirred for about 1 hour while maintaining the temperature at 5 ° C. or lower, then slowly poured into 10000 ml of ice water, and the precipitated crystals were filtered. The crystals were washed with distilled water until no acid remained, and dried to obtain a metal-free tetraazaporphyrin compound represented by the following formula (12) in a yield of 75%.

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The X-ray diffraction spectrum of the tetraazaporphyrin compounds obtained in Production Examples 1 to 10 was measured under the following conditions. X-ray tube Cu (wavelength 1.54 °) Voltage 40 kV Current 20 mA Scanning speed 1 deg / min Scanning range 3 to 40 deg FIGS. 1 to 10 show X-ray diffraction spectra of the tetraazaporphyrin compounds obtained in Production Examples 1 to 10. .

Example 1 1 part by weight of the Mg tetraazaporphyrin compound pigment obtained in Production Example 3 was mixed with a polyvinyl butyral resin (BM-
S, Sekisui Chemical Co., Ltd.) 2% by weight butyl acetate solution 50
Parts by weight and 49 parts by weight of n-butyl acetate were dispersed in a sand mill using glass beads having a diameter of 2 mm for 2 hours. This was applied on a 75 μm aluminum-deposited PET base and dried at 80 ° C. for 5 minutes to form a charge generation layer having a thickness of 0.2 μm. Next, 42 parts by weight of a hole transporting substance represented by the following structural formula (D-1), 60 parts by weight of a polycarbonate resin (Iupilon Z200, manufactured by Mitsubishi Gas Chemical Company), silicone oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) 001 parts by weight were dissolved in 638 parts by weight of dichloromethane to prepare a charge transport layer coating solution. This was applied on the charge generation layer and dried at 80 ° C. for 5 minutes and at 110 ° C. for 10 minutes to form a charge transport layer having a thickness of 20 μm. Thus, an electrophotographic photoreceptor of Example 1 was obtained.

[0078]

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Example 2 Instead of using the pigment obtained in Production Example 3, Production Example 4
An electrophotographic photoreceptor of Example 2 was obtained in the same manner as in Example 1 except that the pigment obtained in the above was used.

Example 3 Instead of using the pigment obtained in Production Example 3, Production Example 5
The electrophotographic photoreceptor of Example 3 was obtained in the same manner as in Example 1 except that the pigment obtained in the above was used.

Example 4 Instead of using the pigment obtained in Production Example 3, Production Example 6
An electrophotographic photoreceptor of Example 4 was obtained in the same manner as in Example 1 except that the pigment obtained in the above was used.

Example 5 Instead of using the pigment obtained in Production Example 3, Production Example 7
An electrophotographic photoreceptor of Example 5 was obtained in the same manner as in Example 1 except that the pigment obtained in the above was used.

Example 6 Instead of using the pigment obtained in Production Example 3, Production Example 9
An electrophotographic photoreceptor of Example 6 was obtained in the same manner as in Example 1, except that the pigment obtained in the above was used.

Example 7 Instead of using the pigment obtained in Production Example 3, Production Example 1
An electrophotographic photosensitive member of Example 7 was obtained in the same manner as in Example 1 except that the pigment obtained in Example 0 was used.

Example 8 Example 8 was repeated except that the hole transport material (D-2) represented by the following structural formula was used in place of the hole transport material (D-1) used in Example 1. In the same manner as in Example 1, an electrophotographic photosensitive member of Example 8 was obtained.

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Example 9 The procedure of Example 1 was repeated except that the hole transport material (D-3) represented by the following structural formula was used instead of the hole transport material (D-1) used in Example 1. In the same manner as in Example 1, an electrophotographic photosensitive member of Example 9 was obtained.

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Example 10 The procedure of Example 1 was repeated, except that the hole transport material (D-1) represented by the following structural formula was used instead of the hole transport material (D-1) used in Example 1. In the same manner as in Example 1, an electrophotographic photosensitive member of Example 10 was obtained.

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Comparative Example 1 The electrophotographic method of Comparative Example 1 was carried out in the same manner as in Example 1 except that the compound obtained in Comparative Production Example was used instead of the pigment obtained in Production Example 3 used in Example 1. I got a body.

<Evaluation> The electrophotographic photosensitive members produced in Examples 1 to 10 and Comparative Example 1 were subjected to two corona discharges at −6 kV using an electrostatic property measuring device EPA-8200 manufactured by Kawaguchi Electric Co., Ltd.
Surface potential Vo (V) after 0 seconds to charge and subsequently dark attenuated for 20 seconds, after exposure to 20 lux of light, exposure amount E _1/2 (lux) required to reduce Vo to 1/2・ Se
c) was measured. Table 18 shows the results.

[0090]

[Table 20]

Example 11 In the same manner as in Example 1, a charge generation layer was formed on an aluminum-deposited PET base. Next, 8 parts by weight of the electron transport material represented by the structural formula (4), 11 parts by weight of polycarbonate Z (manufactured by Teijin Chemicals Limited), and 0.02 parts by weight of silicone oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to tetrahydrofuran 91
This was dissolved in parts by weight, and this was cast and applied on the charge generation layer with a doctor blade and dried to provide a charge transport layer having a thickness of 20 μm. Thus, an electrophotographic photoreceptor of Example 11 was obtained.

Example 12 Example 1 was repeated except that the electron transporting material of the structural formula (8) was used instead of the electron transporting material used in Example 11.
By performing the same operation as in Example 1, an electrophotographic photosensitive member of Example 12 was obtained.

The photoreceptors produced in Examples 11 and 12 were subjected to a corona discharge of +5.3 kV and a corona discharge of 20 using the above-mentioned measuring apparatus.
After charging for 20 seconds, surface potential Vo (V) after dark decay for 20 seconds, and after irradiation with light of 20 lux, Vo is 1
/ _1/2 Exposure E1 _{/ 2} (lux · sec)
Was measured. Table 19 shows the results.

[0094]

[Table 21]

Example 13 0.5 g of the pigment obtained in Production Example 1 was added to 10 g of a polycarbonate Z (manufactured by Teijin Chemicals Ltd.) solution (10 g in tetrahydrofuran).
Ball milling with 9 g of tetrahydrofuran, and then 2% by weight of the pigment composition, 50% by weight of the polycarbonate Z composition, and 28% by weight of the charge transport material (D-1). Then, a 10% by weight polycarbonate Z solution was added to the mixture and stirred sufficiently to prepare a photosensitive layer coating solution. The coating solution thus prepared was cast and applied on a polyester film on which aluminum was deposited by a doctor blade, and the film thickness after drying was 15 μm.
Thus, a single-layer type electrophotographic photoreceptor of Example 13 having m photosensitive layers was obtained.

The electrophotographic photosensitive member produced in Example 13 was charged by performing a corona discharge at -6 kV for 20 seconds using the above-described measuring apparatus, and subsequently, the surface potential Vo (V) after dark decay for 20 seconds. , After irradiation with light of 20 lux, Vo is １ ／
It was measured necessary exposure amount _{E 1/2 (lux · sec} ) to become. Table 20 shows the results.

[0097]

[Table 22]

[0098]

According to the present invention, by using a specific tetraazaporphyrin compound as a charge generating substance for an electrophotographic photoreceptor, an electrophotographic photoreceptor having excellent chargeability and high sensitivity can be provided. For example, a specific tetraazaporphyrin compound can be used as a charge generating substance to provide a highly sensitive laminated or single-layer electrophotographic photoreceptor. Specifically, by using a specific tetraazaporphyrin compound as a charge-generating substance and using a hole-transporting substance or an electron-transporting substance as a charge-transporting substance, to provide a high-sensitivity stacked electrophotographic photoreceptor. Can be. In the electrophotographic photoreceptor, a specific tetraazaporphyrin compound is used as a charge generating substance, and a specific hole transporting substance or a specific electron transporting substance is used as a charge transporting substance, so that a more sensitive stacked type is used. An electrophotographic photoreceptor can be provided.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction spectrum of a tetraazaporphyrin compound obtained in Production Example 1.

FIG. 2 is an X-ray diffraction spectrum of the tetraazaporphyrin compound obtained in Production Example 2.

FIG. 3 is an X-ray diffraction spectrum of the tetraazaporphyrin compound obtained in Production Example 3.

FIG. 4 is an X-ray diffraction spectrum of the tetraazaporphyrin compound obtained in Production Example 4.

5 is an X-ray diffraction spectrum of the tetraazaporphyrin compound obtained in Production Example 5. FIG.

6 is an X-ray diffraction spectrum of the tetraazaporphyrin compound obtained in Production Example 6. FIG.

7 is an X-ray diffraction spectrum of the tetraazaporphyrin compound obtained in Production Example 7. FIG.

8 is an X-ray diffraction spectrum of the tetraazaporphyrin compound obtained in Production Example 8. FIG.

FIG. 9 is an X-ray diffraction spectrum of the tetraazaporphyrin compound obtained in Production Example 9.

FIG. 10 is an X-ray diffraction spectrum of the tetraazaporphyrin compound obtained in Production Example 10.

Continued on the front page (72) Inventor Michihiko Nanba 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (72) Inventor Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Chiaki Tanaka 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (Reference) 2H068 AA19 AA20 AA31 AA34 AA35 BA13 BA14 BA15 BA39 FA12 FA13 FC02

Claims (14)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the following general formula (1), and A, B, and D in the general formula (1). ,
An electrophotographic photoreceptor comprising a tetraazaporphyrin compound wherein at least one of E is A2 and at least one is A1. Embedded image Embedded image Embedded image (In A1, A2, r ₁ ~r ₆ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group or a nitro group, r ₁ And r ₂ and r ₃ to r ₆ may form a ring with each other.
M represents a metal atom, a metal oxide, a metal hydroxide or a metal halide. ) 2. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (1), and A, B, D in the general formula (1). ,
A tetraazaporphyrin compound wherein at least one of E is A2 and at least one is A1 and a tetraazaporphyrin compound wherein all of A, B, D and E in the general formula (1) are A2 An electrophotographic photoreceptor characterized by containing. 3. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer has at least the general formula (1), and further comprises A, B, and D in the general formula (1). ,
A tetraazaporphyrin compound wherein at least one of E is A2 and at least one is A1, and a tetraazaporphyrin compound wherein all of A, B, D and E in the general formula (1) are A1 An electrophotographic photoreceptor characterized by containing. 4. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (1), and A, B, and D in the general formula (1). ,
A tetraazaporphyrin compound in which at least one of E is A2 and at least one is A1, a tetraazaporphyrin compound in which all of A, B, D and E in the general formula (1) are A2; In the general formula (1), A, B,
An electrophotographic photosensitive member comprising: a tetraazaporphyrin compound wherein D and E are all A1. 5. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the following general formula (2), and A, B, and D in the general formula (2). ,
An electrophotographic photoreceptor comprising a tetraazaporphyrin compound wherein at least one of E is A2 and at least one is A1. Embedded image Embedded image Embedded image (In A1, A2, r ₁ ~r ₆ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group or a nitro group, r ₁ And r ₂ and r ₃ to r ₆ may form a ring with each other.) 6. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (2), and A, B, and D in the general formula (2). ,
A tetraazaporphyrin compound wherein at least one of E is A2 and at least one is A1 and a tetraazaporphyrin compound wherein all of A, B, D and E in the general formula (2) are A2 An electrophotographic photoreceptor characterized by containing. 7. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (2), and A, B,
A tetraazaporphyrin compound wherein at least one of D and E is A2 and at least one is A1, and a tetraazaporphyrin compound wherein all of A, B, D and E in the general formula (2) are A1 And an electrophotographic photoreceptor comprising: 8. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by at least the general formula (2);
A tetraazaporphyrin compound wherein at least one of D and E is A2 and at least one is A1, and a tetraazaporphyrin compound wherein all of A, B, D and E in the general formula (2) are A2 And A in the general formula (2)
An electrophotographic photoreceptor comprising: a tetraazaporphyrin compound wherein all of B, D and E are A1. 9. The charge-generating layer according to claim 1, comprising a charge-generating layer containing a charge-generating substance and a charge-transporting layer containing a charge-transporting substance. An electrophotographic photoreceptor comprising a tetraazaporphyrin compound represented by the general formula (1) or (2) according to any one of claims 1 to 8. 10. The electrophotographic photoreceptor according to claim 9, wherein the photosensitive layer comprises: a charge generation layer containing a charge generation substance;
A charge transporting layer containing a hole transporting substance and a charge transporting layer provided on a conductive support in this order. 11. The electrophotographic photoconductor according to claim 10, wherein the hole transporting substance is a stilbene compound represented by the following general formula (3). Embedded image (Wherein, R ₁ and R ₂ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R ₃ and R ₄ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted Represents an aryl group or a heterocyclic group.
₁ and R ₂ may form a ring with each other. Ar ₁ represents a substituted or unsubstituted arylene group or a heterocyclic group. ) 12. The electrophotographic photoreceptor according to claim 9, wherein the photosensitive layer comprises: a charge generation layer containing a charge generation substance;
A positive charge type electrophotographic photoreceptor, comprising: a charge transport layer containing an electron transport material; 13. An electrophotographic photosensitive member according to claim 12, wherein the electron transporting substance is (2,3-diphenyl-1-indenylidene) malononitrile represented by the following formula (4). body. Embedded image 14. The tetraazaporphyrin represented by the general formula (1) or (2) according to any one of claims 1 to 8, wherein the photosensitive layer according to any one of claims 1 to 8 is a charge generating substance. An electrophotographic photoreceptor comprising a single layer containing a compound.